CN106366263A - Linear block copolymer, dendritic nano-silver composite and preparation methods of linear block copolymer and dendritic nano-silver composite - Google Patents
Linear block copolymer, dendritic nano-silver composite and preparation methods of linear block copolymer and dendritic nano-silver composite Download PDFInfo
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- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
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- C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
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Abstract
The invention belongs to the field of nano composites and discloses a linear block copolymer. The structure of the linear block copolymer is shown in the specification, wherein x is larger than or equal to 20 and smaller than or equal to 30, y is larger than or equal to 30 and smaller than or equal to 70, and R is CH3 or CH2CH2OH. The invention further discloses a preparation method of the linear block copolymer, and a dendritic nano-silver composite obtained through self-assembly of the linear block copolymer. The dendritic nano-silver composite has the large specific area and high electrocatalytic activity and has good reduction catalysis capacity to H2O2 and other unstable substances, and therefore the dendritic nano-silver composite can be used as a sensor for detection and analysis of relevant substances.
Description
Technical field
The invention belongs to field of nanocomposite materials, more particularly, to a kind of tree being prepared using linear block copolymers
Dendritic nano silver composite material.
Background technology
It is continuous that nano composite material is typically with matrixes such as polymer (as resin, rubber, fiber etc.), pottery and metals
Phase, metal (nanometer gold, nanometer silver etc.) with nano-scale, quasiconductor, rigid particles or other inorganic particulates, fiber, carbon are received
The modifying agent such as mitron are dispersion phase, by suitable preparation method, modifying agent uniformity are scattered in matrix material, are formed
At least one compound system being existed with nano-scale.
Wherein, nano metal composite is due to the distinctive small-size effect of metal nanoparticle, skin effect, quantum chi
Very little effect and macro quanta tunnel effect etc. make this composite show at aspects such as light, electricity, magnetic, corrosion resistance, catalysis
Very excellent unique property, it has also become the research emphasis of field of nanometer material technology in recent years.Various nano metals of preparing are combined
The method of material is also launched in succession, and progressively tends to improving and ripe.
Nano silver composite material is the polymer composites preparing nanometer modified by silver by introducing polymers functionality, leads to
Each molecule crossing polymer provides multiple connecting portions, acts on nano-Ag particles simultaneously, is effectively fixed,
And the self assembly of various nanostructureds can also be formed by electrostatic, hydrogen bond, electric charge transfer and other effect, to nanoparticle
Play a very good protection.This composite had both been avoided that the limited resource of nano silver material application itself, but also with
Nanometer silver and the double grading of polymer, and impart some new specific performances of composite.Meanwhile, the shape of nanometer silver
Control synthesis can play the performance advantage of this kind of composite further.Prepare the general side of polymer nanocomposite silver composite material
Method has: direct blending, in-situ synthesized, ion exchange, interfacial polymerization etc..
Existing nano silver composite material still has to be hoisted it is therefore desirable to develop a kind of new nanometer in performance at present
Silver composite material.
Content of the invention
It is an object of the invention to provide a kind of linear block copolymers and preparation method thereof.
It is a further object of the present invention to provide a kind of dendritic nano-silver composite and preparation method thereof.
For reaching one of above-mentioned purpose, the present invention employs the following technical solutions:
A kind of linear block copolymers, its structure is
Wherein, 20≤x≤30,30≤y≤70；R is ch3Or ch2ch2oh.
Further, in the structure of linear block copolymers, x: y=1: 1～3.
A kind of method of above-mentioned linear block copolymers, comprises the following steps:
S1, hydroxyethyl methylacrylate and methyl methacrylate are under the conditions of initiator aibn, chain-transferring agent compound 1
Polymerization forms polymer 2；
S2, n- vinyl pyrrolidone is polymerized formation polymer 3 under the conditions of initiator aibn, polymer 2；
S3, polymer 3 obtain polymer 4 through reduction；
Further, compound 1 and the mass ratio of hydroxyethyl methylacrylate are 0.02～0.05: 1.
Further, methyl methacrylate and the mass ratio of hydroxyethyl methylacrylate are 0.01～0.08: 1.
Further, polymer 2 and the mass ratio of n- vinyl pyrrolidone are 0.1～0.2: 1.
Further, the reaction temperature of step s1 is 50～70 DEG C, and the reaction temperature of step s2 is 60～80 DEG C.
A kind of dendritic nano-silver composite, is formed with nanometer silver self assembly by above-mentioned linear block copolymers.
A kind of method preparing above-mentioned dendritic nano-silver composite, comprises the following steps:
A1, linear block copolymers are made the aqueous solution of 1～3wt%；
A2, in aqueous solution add silver nitrate, after mix homogeneously add reducing agent, stir 3～10min；
Load bag filter after a3, standing 20～30h, use ethanol, deionized water to dialyse successively 3～7 days, after lyophilization
To nano silver composite material.
Further, the consumption of silver nitrate is the 1～3% of linear block copolymers quality, and silver nitrate is rubbed with reducing agent
Your ratio is 1:1.2～1.5.
The present invention with compound 1 for the required chain-transferring agent of polymerization, be sequentially prepared the first block copolymer (polymer 2),
Di-block copolymer (polymer 3), finally obtains subject polymer after carrying out reduction.
The present invention prepares the block copolymer 3 of ad hoc structure by raft polymerization, obtains target block copolymer after carrying out reduction
4, using block copolymer 4 self assembly, the composite containing dendritic nano-silver can be prepared.Many researchs demonstrate raft polymerization
Mechanism, the control mechanism of existing well accepted raft polymerization is: the primary group of free radicals being produced by decomposition of initiator is anti-with monomer
Should after form Propagating Radical pn, carbon sulfur double bond in Propagating Radical and raft reagent (i.e. compound 1 in the present invention)
Additive reaction is occurred to form unstable free radical intermediate.This free radical intermediate can decompose its reactant of generation, or
It is decomposed to form the dormancy polymer of temporary transient inactivation, produce r free radical simultaneously.Free radical r can be gathered trigger monomer again
Close.The dormancy polymer ends producing are decomposed by intermediate and contains dithio carbonyl structure (- s (s) c-z), it can also conduct
Chain-transferring agent and other free radical react.Propagating Radical and macromole raft reagent reacting, original Propagating Radical
Form dormancy polymer, and the dormancy polymer in macromole raft reagent forms new Propagating Radical and can occur further
Reaction of propagation.The new dormancy polymer being formed can be reacted with Propagating Radical as macromole raft reagent again and be lived
Change.Because these processes are all reversible processes, such that it is able to control Propagating Radical concentration in polymerization system.
The method have the advantages that
Nano silver composite material can be used as catalyst, the catalysis of photomechanical production, surface enhanced raman spectroscopy and multiple reaction
Agent etc..The dendritic nano-silver material of the present invention has larger specific surface area and higher electro catalytic activity, to h2o2Deng unstable
Earnest matter has good reduction catalystses ability, because the detection and analysis of related substanceses can be used for as sensor.For example:
1st, dendritic nano-silver has good Raman enhancement effect for DNA (deoxyribonucleic acid), ribonucleic acid, Folic Acid, right
The detectable concentration of three kinds of detectable substances can reach 10-12mol/l.Therefore, it can pass as overdelicate surface Raman enhancement spectrum
Sensor probe, for unmarked analysis detection biomacromolecule.
When the 2nd, using dendritic nano-silver electrode detection formaldehyde, its detection sensitivity s is 0.27ma.cm-3, its Monitoring lower-cut is
0.662mmol.l-1, can be used as the electrochemical sensor of detection formaldehyde.
3rd, nanometer silver granules show the electrocatalytic oxidation activity special to glucose, and its corresponding detection is sensitive
Spend for 0.57ma.cm-3, Monitoring lower-cut be 13.94 μm of ol.l-1, and detect glucose when, Ascorbic Acid, hydrogen peroxide,
The anti-interference of Glutathione, sucrose and Lactose etc. is stronger, shows that it has good electro-catalysis and lives to the electroxidation of glucose
Property, this electrode can be used for detecting the glucose of low concentration as sensor, be applied to the Rapid Screening of diabetes.
Brief description
Fig. 1 is embodiment 1 chain-transferring agent1H nmr collection of illustrative plates；
Fig. 2 is embodiment 1 chain-transferring agent13C nmr collection of illustrative plates；
Fig. 3 is the ms collection of illustrative plates of embodiment 1 chain-transferring agent；
Fig. 4 is the ft-ir collection of illustrative plates of embodiment 1 chain-transferring agent；
Fig. 5 is the ft-ir collection of illustrative plates of embodiment 2 polymer 2 and polymer 3；
Fig. 6 is embodiment 2 polymer 2 and polymer 31H nmr collection of illustrative plates；
Fig. 7 is the x-ray diffraction collection of illustrative plates of embodiment 3 nano silver composite material；
Fig. 8 is the Raman spectrogram of embodiment 3 nano silver composite material；
Fig. 9 is the photoelectron spectroscopy figure of the oxygen element of embodiment 3 nano silver composite material；
Figure 10 is the photoelectron spectroscopy figure of the carbon of embodiment 3 nano silver composite material；
Figure 11 is the full spectrogram of xps of embodiment 3 nano silver composite material；
Figure 12 is the transmission electron microscope figure of embodiment 3 nano silver composite material；
Figure 13 is the transmission electron microscope figure of comparative example nano silver composite material.
Specific embodiment
The self-assembly that block copolymer is formed or the method that characterized of polymer based nanocomposites, document
That reports is a lot, and characterization method of the present invention has: infrared spectrum (ft-ir), Raman spectrum (raman), nuclear magnetic resonance, NMR
Spectrum (nmr), transmission electron microscope (tem), scanning electron microscope (sem), photoelectron spectroscopy (xps), Dynamic laser scattering (dls), difference scanning
Calorimetric (dsc) and x-ray diffraction (xrd).
Infrared spectrum (ft-ir): for solid sample, frequently with kbr and solid sample mixed pressuring plate method, for grease
Can be using the coating method on kbr piece；Need through fully dry before sample testing, using the pectrum 100 of pe company of the U.S.
Infrared spectrometer, is tested in constant-temperature constant-humidity environment, and its spectral region is 4000～450cm-1, spectral resolution is better than
0.09cm-1, scan 3 times.
Nuclear magnetic resoance spectrum (nmr): for small molecule sample, take 5mg sample, be placed in nuclear magnetic tube, add 0.5ml deuterium
For solvent, shaking is allowed to fully dissolve；For synthetic product macromolecular sample (block copolymer), take 15mg sample, put
In nuclear magnetic tube, suitable deuterated solvent is selected respectively according to structure, shaking is allowed to fully dissolve.Using German bruker company
Avance (400mhz) tested, collect sample1H spectrum and13C composes.
Transmission electron microscope (tem): by sample to be tested dissolving or dispersed in a suitable solvent, directly take a little
Drop on special copper mesh, observed on the jem-2100 (tem) of Japanese jeol company after naturally drying.If desired observe
The special appearances such as " nucleocapsid " micelle, then can increase dyeing procedure during making copper mesh specimen, such as can be by glue with phosphotungstic acid
Hydrophilic polymer layer in bundle dyes dark color.
Scanning electron microscope (sem): sample to be tested, after being fully dried, needs to carry out vacuum metal spraying process, then
Ultra-55 (sem) using German zeiss company is observed.
Photoelectron spectrograph (xps): using the photoelectron spectrograph escalab 250 of thermo fisher company of the U.S.
Tested, using x-ray source for monochromatization alk α source (mono alk α), energy be 1486.6ev, 15kv 150w, beam spot is big
Little is 500 μm, cae scan pattern, and Lens-Mode is large area xl, and during full spectrum scanning, setting is logical can be 150ev, narrow spectrum
Arranging logical during scanning can be 20ev.
FTRaman SpectrometerFTIRRaman (raman): using thermo fisher company of U.S. Raman spectrometer
Nicolet nxr9650 is tested, and excitation wavelength is 1064nm, and spectral resolution is 0.8cm-1, sweep limitss are set to 50
～3500cm-1.
X-ray diffraction instrument (xrd): the x-ray diffraction instrument empyrean using Dutch PANalytical company is tested, power
3kw, scanning speed is 10 °/min, and 10 °～70 ° of measurable angle range (2 θ) scans 3 times.
Embodiment 1
The synthesis of chain-transferring agent
Synthesize chain-transferring agent according to above reaction equation, these reactions are known popular response, can be according to common anti-
Answer condition to carry out, repeat no more.
Chain-transferring agent1H nmr collection of illustrative plates as shown in figure 1,13C nmr collection of illustrative plates is as shown in Fig. 2 ms collection of illustrative plates is as shown in figure 3, ft-
Ir collection of illustrative plates is as shown in figure 4, the provable synthesis of these characterize datas has obtained chain-transferring agent.
Embodiment 2
The synthesis of linear block copolymers
1st, add 0.04g chain-transferring agent compound 1 in 100ml there-necked flask, after evacuation 15min under ice-water bath, lead to nitrogen
Gas 15min, 3 times repeatedly, is warmed to room temperature, and when observation system gradually becomes blackish green, adds 0.8g initiator aibn, 0.05g methyl-prop
E pioic acid methyl ester and 1g monomers hydroxy ethyl ester, 65 DEG C of isothermal reaction 3h, liquid nitrogen terminating reaction.With chloroform for precipitation
Agent separate, after with ethanol dissolving, dissolving-precipitation operation realizes purification 3 times repeatedly, to polymer 2.
2nd, add 0.15g polymer 2 in reaction bulb, nitrogen protection is lower to add 0.8g initiator aibn, 1g n- vinyl
Ketopyrrolidine, 70 DEG C of isothermal reaction 4h, liquid nitrogen terminating reaction.With acetone for precipitant separately, with ethanol dissolving after, repeatedly molten
Solution-precipitation operation realizes purification 3 times, to polymer 3.
3rd, polymer 3 is dissolved in appropriate deionized water, under room temperature condition, add the nabh of 1.2 times of meterings4, stirring is simultaneously
Sustained response 1h；Then, with acetone for precipitant separately, with ethanol dissolving after, dissolving-precipitation operation realizes purification 2 times repeatedly,
To polymer 4.
In structural formula, x=26, y=55, r are ch3Or ch2ch2oh.
The ft-ir collection of illustrative plates of polymer 2 and polymer 3 increases, in polymer 2 as shown in figure 5, working as hema polymerized unit proportion
- oh content also accordingly increase, corresponding to ft-ir in figure 3200～3500cm-1- oh the absorption peak strength at place increases；Work as introducing
After n- vinyl pyrrolidone fragment, due to the hydrogen bond action of-oh in the n in ketopyrrolidine and the first block, make correspondence position
Absworption peak peak type accordingly broadens.Therefore can be with inference: polymer 3 has the hydrophobic block that two kinds of units of hema and mma are constituted and nvp
The hydrophilic block being polymerized.The nuclear magnetic spectrum (Fig. 6) of polymer 2 and polymer 3 also proves this conclusion simultaneously.
Embodiment 3
The self assembly of dendritic nano-silver composite
1st, the linear block copolymers obtaining embodiment 2 make the aqueous solution of 2wt%, and block copolymer is in aqueous
Nano-micelle can be self-assembled into, the wherein relative lipophile segment containing certain hydroxyl constitutes the kernel of micelle, hydrophilic segment
Constitute the shell of micelle, this structure is subsequently to provide " nanometer device "；
2nd, add silver nitrate in aqueous solution, after mix homogeneously, under room temperature, add reducing agent, stir 6min, solution is gradually
It is changed into light brown from colourless；The consumption of silver nitrate is the 2% of linear block copolymers quality, the mol ratio of silver nitrate and reducing agent
It is 1:1.4, reducing agent is hydrazine；
3rd, load bag filter after standing 24h, use ethanol, deionized water to dialyse successively 5 days, after lyophilization, obtain nanometer silver
Composite.
The x-ray diffraction of nano silver composite material as shown in fig. 7, the size of nano-Ag particles is little and be uniformly distributed, so
Have but inconspicuous in the signal peak of in figure correspondence position.
Nano silver composite material carry out Raman spectrum test, as shown in figure 8, the carbonyl in nanometer silver and polymer architecture
There is certain complexing, 1400～1500cm in base, hydroxyl-1The change at place peak is because hydroxyl and the nanometer silver phase of polymer
Caused by interaction；648cm-1The peak at place shows the presence of nanometer silver in sample.
As shown in figure 9, curve a is polymer 4, curve b is to receive to the photoelectron spectroscopy of the oxygen element of nano silver composite material
Rice silver composite material, the photoelectron spectroscopy of element embodies the chemical environment residing for each element atom in material, when ag and nanometer
Silver composite material carboxyl, hydroxyl form complexing, and the signal peak of oxygen element occurs a certain degree of displacement.The photoelectricity of carbon
As shown in Figure 10, curve a is polymer 4 to sub- power spectrum, and curve b is nano silver composite material, signal peak near 287ev.
The full spectrogram of xps of nano silver composite material is as shown in figure 11 it is seen that each object element all exists.
By above characterization method it was demonstrated that nano silver composite material is obtained by self assembly.
As shown in figure 12, its complexion is in dendroid to the transmission electron microscope figure of nano silver composite material.
It can be seen that, using the self assembly characteristic of linear block copolymers polymer 4, by regulating and controlling preparation technology, can hold very much
Preparation of changing places has the nano silver composite material of special appearance.
Nano silver grain is a kind of particularly useful material, such as catalyst, photomechanical production, surface enhanced raman spectroscopy
And the catalyst of multiple reaction etc..The quality of catalytic performance depends on the size and dimension of metal nano material.Dendroid nanometer
The mechanism that is electrochemically formed of silver-colored structure is mainly the moment nucleation of silver atoms and anisotropic growth gained.
Because dendritic nano-silver material has larger specific surface area and higher electro catalytic activity, to h2o2Deng unstable
Earnest matter has good reduction catalystses ability, because the detection and analysis of related substanceses can be used for as sensor.For example:
1st, dendritic nano-silver has good Raman enhancement effect for DNA (deoxyribonucleic acid), ribonucleic acid, Folic Acid, right
The detectable concentration of three kinds of detectable substances can reach 10-12mol/l.Therefore, it can pass as overdelicate surface Raman enhancement spectrum
Sensor probe, for unmarked analysis detection biomacromolecule.
When the 2nd, using dendritic nano-silver electrode detection formaldehyde, its detection sensitivity s is 0.27ma.cm-3, its Monitoring lower-cut is
0.662mmol.l-1, can be used as the electrochemical sensor of detection formaldehyde.
3rd, nanometer silver granules show the electrocatalytic oxidation activity special to glucose, and its corresponding detection is sensitive
Spend for 0.57ma.cm-3, Monitoring lower-cut be 13.94 μm of ol.l-1, and detect glucose when, Ascorbic Acid, hydrogen peroxide,
The anti-interference of Glutathione, sucrose and Lactose etc. is stronger, shows that it has good electro-catalysis and lives to the electroxidation of glucose
Property, this electrode can be used for detecting the glucose of low concentration as sensor, be applied to the Rapid Screening of diabetes.
Comparative example
With linear block copolymers p (aa-co-mma)-b-pvp (poly acrylic acid-poly methyl methacrylate-polyvinyl
Ketopyrrolidine macromolecular chain, with reference to Master's thesis: Liang Runcheng, the synthesis of amphipathic beta-schardinger dextrin-star-type polymer and its micelle are given
The research of medicine body system, Guangdong Pharmaceutical University, 2013), Sargassum polysaccharides base graft-type block copolymer sa-330-s29 (reference: Liu
Meaning, Wu Shikai, Li Jinwei etc., the preparation of Sargassum polysaccharides group block copolymer/nano-Au composite, ACAD J GCP,
2014,30 (4): 408-412), homopolymer pvp carries out contrast experiment, with reference to the method for embodiment 3, prepares respectively and gathers accordingly
Compound base nano silver composite material a, b or c, as shown in figure 13, (a) is nano silver composite material a, and (b) is nanometer silver composite wood
Material b, (c) is nano silver composite material c, and the nano-Ag particles of these composites are all subsphaeroidal or other pattern is it is impossible to from group
Dress up dendroid, and by adjusting polymer and agno3Contrast consumption, nor obtain dendritic nanometer silver composite wood
Material.
Embodiment 4
First, first synthesizing linear block copolymer (with reference to the reaction equation of embodiment 3)
1st, add 0.02g chain-transferring agent compound 1 in 100ml there-necked flask, after evacuation 15min under ice-water bath, lead to nitrogen
Gas 15min, 3 times repeatedly, is warmed to room temperature, and when observation system gradually becomes blackish green, adds 0.5g initiator aibn, 0.02g methyl-prop
E pioic acid methyl ester and 1g monomers hydroxy ethyl ester, 52 DEG C of isothermal reaction 3h, liquid nitrogen terminating reaction.With chloroform for precipitation
Agent separate, after with ethanol dissolving, dissolving-precipitation operation realizes purification 3 times repeatedly, to polymer 2.
2nd, add 0.11g polymer 2 in reaction bulb, nitrogen protection is lower to add 0.5g initiator aibn, 1g n- vinyl
Ketopyrrolidine, 63 DEG C of isothermal reaction 2.5h, liquid nitrogen terminating reaction.With acetone for precipitant separately, with ethanol dissolving after, repeatedly molten
Solution-precipitation operation realizes purification 3 times, to polymer 3.
3rd, polymer 3 is dissolved in appropriate deionized water, under room temperature condition, add the vitamin c of 1.2 times of meterings, stirring
And sustained response 1h；Then, with acetone for precipitant separate, after with ethanol dissolving, repeatedly dissolving-precipitation operation realize for 2 times pure
Change, to polymer 4.
In structural formula, x=21, y=63, r are ch3Or ch2ch2oh.
2nd, self assembly obtains dendritic nano-silver composite
1st, the linear block copolymers obtaining embodiment 2 make the aqueous solution of 1wt%, and block copolymer is in aqueous
Nano-micelle can be self-assembled into, the wherein relative lipophile segment containing certain hydroxyl constitutes the kernel of micelle, hydrophilic segment
Constitute the shell of micelle, this structure is subsequently to provide " nanometer device "；
2nd, add silver nitrate in aqueous solution, after mix homogeneously, under room temperature, add reducing agent, stir 4min, solution is gradually
It is changed into light brown from colourless；The consumption of silver nitrate is the 1～3% of linear block copolymers quality, and silver nitrate is rubbed with reducing agent
Your ratio is 1:1.2, and reducing agent is sodium borohydride；
3rd, load bag filter after standing 22h, use ethanol, deionized water to dialyse successively 4 days, after lyophilization, obtain nanometer silver
Composite.
Embodiment 5
First, first synthesizing linear block copolymer (with reference to the reaction equation of embodiment 3)
1st, add 0.05g chain-transferring agent compound 1 in 100ml there-necked flask, after evacuation 15min under ice-water bath, lead to nitrogen
Gas 15min, 3 times repeatedly, is warmed to room temperature, and when observation system gradually becomes blackish green, adds 1g initiator aibn, 0.08g metering system
Sour methyl ester and 1g monomers hydroxy ethyl ester, 70 DEG C of isothermal reaction 5h, liquid nitrogen terminating reaction.With chloroform as precipitant
Separately, with ethanol dissolving after, dissolving-precipitation operation realizes purification 3 times repeatedly, to polymer 2.
2nd, add 0.2g polymer 2 in reaction bulb, nitrogen protection is lower to add 1g initiator aibn, 1g n- vinylpyridine
Pyrrolidone, 78 DEG C of isothermal reaction 5h, liquid nitrogen terminating reaction.With acetone for precipitant separately, with ethanol dissolving after, repeatedly dissolve-
Precipitation operation realizes purification 3 times, to polymer 3.
3rd, polymer 3 is dissolved in appropriate deionized water, add the hydrazine of 1.2 times of meterings under room temperature condition, stirring is simultaneously
Sustained response 1h；Then, with acetone for precipitant separately, with ethanol dissolving after, dissolving-precipitation operation realizes purification 2 times repeatedly,
To polymer 4.
In structural formula, x=30, y=30, r are ch3Or ch2ch2oh.
2nd, self assembly obtains dendritic nano-silver composite
1st, the linear block copolymers obtaining embodiment 2 make the aqueous solution of 3wt%, and block copolymer is in aqueous
Nano-micelle can be self-assembled into, the wherein relative lipophile segment containing certain hydroxyl constitutes the kernel of micelle, hydrophilic segment
Constitute the shell of micelle, this structure is subsequently to provide " nanometer device "；
2nd, add silver nitrate in aqueous solution, after mix homogeneously, under room temperature, add reducing agent, stir 3～10min, solution
Gradually it is changed into light brown from colourless；The consumption of silver nitrate is the 1～3% of linear block copolymers quality, silver nitrate and reducing agent
Mol ratio be 1: 1.5, reducing agent be sodium borohydride；
3rd, load bag filter after standing 30h, use ethanol, deionized water to dialyse successively 7 days, after lyophilization, obtain nanometer silver
Composite.
The above, the only specific embodiment of the present invention, but protection scope of the present invention is not limited thereto, and any
Belong to those skilled in the art the invention discloses technical scope in, the change or replacement that can readily occur in, all answer
It is included within the scope of the present invention.Therefore, protection scope of the present invention should be defined by scope of the claims.
Claims (10)
1. a kind of linear block copolymers are it is characterised in that its structure is
Wherein, 20≤x≤30,30≤y≤70；R is ch3Or ch2ch2oh.
2. linear block copolymers according to claim 1 are it is characterised in that x: y=1: 1～3.
3. a kind of method of the linear block copolymers prepared described in claim 1 is it is characterised in that comprise the following steps:
S1, hydroxyethyl methylacrylate and methyl methacrylate are polymerized under the conditions of initiator aibn, chain-transferring agent compound 1
Form polymer 2；
S2, n- vinyl pyrrolidone is polymerized formation polymer 3 under the conditions of initiator aibn, polymer 2；
S3, polymer 3 obtain polymer 4 through reduction；
Wherein, 20≤x≤30,30≤y≤70；R is ch3Or ch2ch2oh.
4. method according to claim 3 is it is characterised in that compound 1 with the mass ratio of hydroxyethyl methylacrylate is
0.02～0.05: 1.
5. method according to claim 3 is it is characterised in that the matter of methyl methacrylate and hydroxyethyl methylacrylate
Amount ratio is 0.01～0.08: 1.
6. method according to claim 3 is it is characterised in that polymer 2 with the mass ratio of n- vinyl pyrrolidone is
0.1～0.2: 1.
7. method according to claim 3 is it is characterised in that the reaction temperature of step s1 is 50～70 DEG C, step s2
Reaction temperature is 60～80 DEG C.
8. a kind of dendritic nano-silver composite it is characterised in that by the linear block copolymers described in claim 1 with receive
The silver-colored self assembly of rice forms.
9. a kind of method of the dendritic nano-silver composite prepared described in claim 8 is it is characterised in that include following walking
Rapid:
A1, linear block copolymers are made the aqueous solution of 1～3wt%；
A2, in aqueous solution add silver nitrate, after mix homogeneously add reducing agent, stir 3～10min；
Load bag filter after a3, standing 20～30h, use ethanol, deionized water to dialyse successively 3～7 days, received after lyophilization
Rice silver composite material.
10. method according to claim 9 is it is characterised in that the consumption of silver nitrate is the 1 of linear block copolymers quality
～3%, silver nitrate is 1: 1.2～1.5 with the mol ratio of reducing agent.
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